ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermochemical kinetics formulation of conventional transition state theory has been applied to metathesis reactions of H atoms with a series of alkanes in order to provide a sound framework for the intercomparison of experimental data, and also to extrapolate rate coefficients to temperature regimes that may lie beyond the range of experiments. The calculations require a value for the rate coefficient at some temperature, necessitating a discussion of the extant experimental data and their reliability. The procedures are described, the results of the calculations are presented, and their agreement with experimental data (for methane, ethane, propane, butane, pentane, isobutane, cyclopropane, cyclohexane, neopentane, neooctane, and 2,2,3-trimethylbutane) is discussed. A general expression for reactions of H with large (more than 4 carbons) alkanes is proposed: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{rcl} k({\rm T}) &=& 5.4\, \times\, 10^3 n_p {\rm T}^{{\rm 2.0}} \exp (- 3540/{\rm T)}\, +\, 4.7\, \times\, 10^3 n_s {\rm T}^{{\rm 2}{\rm .2}} \exp (- 2640/{\rm T)}\\ \,\,&+&\, 3.7\, \times\, 10^3 n_t {\rm T}^{{\rm 2}{\rm .0}} \exp (- 970/{\rm T),} \end{array} $$\end{document} where np, ns, and nt are the numbers of primary, secondary, and tertiary H atoms available for abstraction.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550230804
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